Crosslinked polymers with amine binding groups

ABSTRACT

Crosslinked polymeric materials are described that contain pendant amine capture groups. The amine capture groups include N-sulfonyldicarboximide groups that can react with amine-containing materials by a ring opening reaction. Reaction mixtures used to prepare the crosslinked polymeric materials, articles containing the crosslinked polymeric materials, methods of making articles, and methods of immobilizing an amine-containing material are also described.

TECHNICAL FIELD

Crosslinked polymeric materials having pendant amine capture groups,articles containing the crosslinked polymeric materials, and methods ofimmobilizing an amine-containing material are described.

BACKGROUND

Amine-containing materials such as amine-containing analytes, aminoacids, DNA, RNA, proteins, cells, tissue, organelles, immunoglobins, orfragments thereof immobilized on a surface can be used in numerousapplications. For example, immobilized biological amines can be used forthe medical diagnosis of a disease or genetic defect, for biologicalseparations, or for detection of various biomolecules. Immobilization ofthe amine containing material is typically accomplished by reaction ofan amino group with an amine reactive functional group that iscovalently attached to the surface of the substrate.

Such amine reactive surfaces can be prepared, for example, by coatingonto the surface of a substrate a solution of a polymeric materialprepared from an amine reactive monomer such asN-[(meth)acryloxy]succinimide or vinyl azlactone. An amine-containingmaterial can react with the N-acyloxysuccinimide group resulting indisplacement of N-hydroxysuccinimide and formation of a carboxamide. Anamine-containing material can react with the cyclic azlactone resultingin an opening of the ring structure.

Although polymeric surfaces that include a reactive functional groupsuch as an N-acyloxysuccinimide group or an azlactone group can reactreadily with primary or secondary amine-containing materials, suchreactive functional groups can suffer from a number of disadvantages.For example, many of the reactions with biological amines are conductedin dilute aqueous solutions. Under these conditions, theN-acyloxysuccinimide functional group is known to undergo rapidhydrolysis. This competing reaction can cause incomplete or inefficientimmobilization of the amine-containing materials on the substrate.

While azlactone functional groups are more stable to hydrolysis, it isdifficult to synthesize an azlactone linked to any polymerizable groupother than a vinyl group. This results in polymeric material with theamine reactive functional group directly attached to the polymerbackbone. This can make it difficult for the amine containing materialto get close enough to the amine reactive group for efficientimmobilization.

A need exists for polymeric materials with alternative amine reactivefunctional groups that can be used as coatings for the immobilization ofamine-containing materials and that have good adhesion to a substrate.

SUMMARY

Reaction mixtures and crosslinked polymeric materials formed from thereaction mixtures are described. More specifically, the reactionmixtures and the crosslinked polymeric materials contain amine capturegroups. The amine capture groups include N-sulfonyldicarboximide groupsthat can react with amine-containing materials by a ring openingreaction. Articles containing the crosslinked polymeric material,methods of making the articles, and methods of immobilizing anamine-containing material are also described.

In a first aspect, a reaction mixture is described that includes (a) anamine capture monomer of Formula I

and (b) a crosslinking monomer that includes at least two (meth)acryloylgroups. The amine capture monomer of Formula I can be unsubstituted orsubstituted with a halo, alkyl, alkoxy, or combinations thereof. InFormula I,

-   -   R¹ and R² together with a dicarboximide group to which they are        attached form a four to eight membered heterocyclic or        heterobicyclic group that can be fused to an optional aromatic        group, optional saturated or unsaturated cyclic group, or        optional saturated or unsaturated bicyclic group;    -   R³ is hydrogen or methyl;    -   R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or        alkylsulfonyl;    -   L is an oxy or —NR⁴—; and    -   Y is a divalent group comprising an alkylene, heteroalkylene,        arylene, or combinations thereof.

In a second aspect, a crosslinked polymeric material is described thatincludes the reaction product of a reaction mixture that contains (a) anamine capture monomer of Formula I and (b) a crosslinking monomer thatincludes at least two (meth)acryloyl groups.

In a third aspect, an article is described that includes a substrate anda crosslinked polymeric material disposed on a surface of the substrate.The crosslinked polymeric material includes the reaction product of areaction mixture that contains (a) an amine capture monomer of Formula Iand (b) a crosslinking monomer that includes at least two (meth)acryloylgroups. The crosslinked polymeric material has a pendant amine capturegroup that includes a N-sulfonyldicarboximide group.

In a fourth aspect, a method of making an article is described. Themethod includes providing a substrate, disposing a reaction mixture on asurface of the substrate, and curing the reaction mixture to form acrosslinked polymeric material. The reaction mixture contains (a) anamine capture monomer of Formula I and (b) a crosslinking monomer thatincludes at least two (meth)acryloyl groups. The crosslinked polymericmaterial has a pendant amine capture group that includes aN-sulfonyldicarboximide group.

In a fifth aspect, a method of immobilizing an amine-containing materialis described. The method includes providing a substrate, and disposing areaction mixture on a surface of the substrate. The reaction mixturecontains (a) an amine capture monomer of Formula I and (b) acrosslinking monomer that includes at least two (meth)acryloyl groups.The method further includes curing the reaction mixture to form acrosslinked polymeric material having a pendant amine capture group thatincludes a N-sulfonyldicarboximide group, and reacting anamine-containing material with the N-sulfonyldicarboximide group.

In a sixth aspect, a polymeric material is provided that includespendant groups of Formula II

wherein

-   -   L is an oxy or —NR⁴—;    -   R¹ and R² together with a dicarboximide group to which they are        attached form a four to eight membered heterocyclic or        heterobicyclic group that can be fused to an optional aromatic        group, optional saturated or unsaturated cyclic group, or        optional saturated or unsaturated bicyclic group;    -   R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or        alkylsulfonyl;    -   Y is a divalent group comprising an alkylene, heteroalkylene,        arylene, or combinations thereof;    -   an asterisk (*) denotes an attachment site of the pendant group        to a backbone of the polymeric material;    -   the pendant group of Formula II is unsubstituted or substituted        with a halo, alkyl, alkoxy, or combinations thereof; and    -   the polymeric material is crosslinked.

In a seventh aspect, a polymeric material is provided that includespendant groups of Formula III

-   -   L is an oxy or —NR⁴—;    -   R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or        alkylsulfonyl;    -   R⁵ is an alkylene having 1 to 5 carbon atoms, aromatic group,        saturated or unsaturated cyclic group, saturated or unsaturated        bicyclic group, or combination thereof;    -   T is equal to a primary amine-containing biological material        minus a H₂N— group;    -   Y is a divalent group comprising an alkylene, heteroalkylene,        arylene, or combinations thereof;    -   an asterisk (*) denotes an attachment site of the pendant group        to a backbone of the polymeric material;    -   the pendant group of Formula III is unsubstituted or substituted        with a halo, alkyl, alkoxy, or combinations thereof; and    -   the polymeric material is crosslinked.

The terms “a”, “an”, and “the” are used interchangeably with “at leastone” to mean one or more of the elements being described.

The term “acyl” refers to a monovalent group of formula —(CO)R where Ris an alkyl group and where (CO) used herein indicates that the carbonis attached to the oxygen with a double bond.

The term “alkoxy” refers to a monovalent group of formula —OR where R isan alkyl group.

The term “alkyl” refers to a monovalent group that is a radical of analkane and includes groups that are linear, branched, cyclic, orcombinations thereof. The alkyl group typically has 1 to 30 carbonatoms. In some embodiments, the alkyl group contains 1 to 20 carbonatoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbonatoms. Examples of alkyl groups include, but are not limited to, methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl,n-hexyl, cyclohexyl, n-heptyl, n-octyl, and ethylhexyl.

The term “alkylene” refers to a divalent group that is a radical of analkane. The alkylene can be straight-chained, branched, cyclic, orcombinations thereof. The alkylene typically has 1 to 30 carbon atoms.In some embodiments, the alkylene contains 1 to 20, 1 to 10, 1 to 6, or1 to 4 carbon atoms. The radical centers of the alkylene can be on thesame carbon atom (i.e., an alkylidene) or on different carbon atoms.

The term “alkylsulfonyl” refers to a monovalent group of formula —SO₂Rwhere R is an alkyl.

The term “amine capture monomer” refers to a monomer having an aminecapture group. The term “amine capture” refers to a group on a monomeror polymeric material that is capable of reacting with anamine-containing material. The amine capture group often includes aN-sulfonyldicarboximide group.

The term “amine-containing material” refers to a material that has aprimary amine group, a secondary amine group, or a combination thereof.The amine-containing material can be a biological material or anon-biological material. The amine-containing material often has analkylene group attached to the primary amine group, secondary aminegroup, or a combination thereof.

The term “aralkyl” refers to a monovalent group that is a radical of thecompound R—Ar where Ar is an aromatic carbocyclic group and R is analkyl group.

The term “aryl” refers to a monovalent group that is aromatic andcarbocyclic. The aryl can have one to five rings that are connected toor fused to the aromatic ring. The other ring structures can bearomatic, non-aromatic, or combinations thereof. Examples of aryl groupsinclude, but are not limited to, phenyl, biphenyl, terphenyl, anthryl,naphthyl, acenaphthyl, anthraquinonyl, phenanthryl, anthracenyl,pyrenyl, perylenyl, and fluorenyl.

The term “arylsulfonyl” refers to a monovalent group of formula —SO₂Arwhere Ar is an aryl.

The term “arylene” refers to a divalent group that is carbocyclic andaromatic. The group has one to five rings that are connected, fused, orcombinations thereof. The other rings can be aromatic, non-aromatic, orcombinations thereof. In some embodiments, the arylene group has up to 5rings, up to 4 rings, up to 3 rings, up to 2 rings, or one aromaticring. For example, the arylene group can be phenylene.

The term “carbonyl” refers to a divalent group of formula —(CO)—.

The term “carbonylimino” refers to a divalent group of formula—(CO)NR^(b)— where R^(b) is hydrogen, alkyl, aryl, aralkyl, acyl,alkylsulfonyl, or arylsulfonyl.

The term “carbonyloxy” refers to a divalent group of formula —(CO)O—.

The term “dicarboximide” refers to a trivalent group of formula

The term “halo” refers to fluoro, chloro, bromo, or iodo.

The term “heteroalkylene” refers to a divalent alkylene having one ormore —CH₂— groups replaced with a thio, oxy, or —NR^(a)— where R^(a) ishydrogen or alkyl. The heteroalkylene can be linear, branched, cyclic,or combinations thereof and can include up to 60 carbon atoms and up to15 heteroatoms. In some embodiments, the heteroalkylene includes up to50 carbon atoms, up to 40 carbon atoms, up to 30 carbon atoms, up to 20carbon atoms, or up to 10 carbon atoms.

The term “(meth)acrylate” refers to monomer that is an acrylate ormethacrylate. Likewise, the term “(meth)acrylamide” refers to a monomerthat is an acrylamide or a methacrylamide.

The term “(meth)acryloyl” group refers to an ethylenically unsaturatedgroup of formula CH₂═CR^(c)—(CO)— where R^(c) is hydrogen or methyl.

The term “N-sulfonyldicarboximide” refers to a trivalent entity offormula

The term “oxy” refers to a divalent group of formula —O—.

The term “pendant” when referring to a polymeric material means a groupthat is attached to the backbone of the polymeric material but that isnot part of the backbone of the polymeric material. The pendant group isnot involved in the polymerization reaction. For example, the group Q isthe pendant group in a polymer formed by free radical polymerization ofa reaction mixture that includes ethylenically unsaturated monomers offormula CH₂═C(R^(x))-Q. In this monomer formula, R^(x) is a hydrogen,alkyl, or aryl and Q is a group attached to the ethylenicallyunsaturated group.

The term “polymer” refers to both materials prepared from one monomersuch as a homopolymer or to materials prepared from two or more monomerssuch as a copolymer, terpolymer, or the like. Likewise, the term“polymerize” refers to the process of making a polymeric material thatcan be a homopolymer, copolymer, terpolymer, or the like.

The term “thio” refers to a divalent group of formula —S—.

The term “room temperature” refers to a temperature of about 20° C. toabout 25° C. or about 22° C. to about 25° C.

A curve connecting two groups in a formula indicates that the two groupstogether form part of a structure that can be cyclic. That is, the twogroups are linked together. A line intersecting this curve indicates acovalent bond to an atom in the structure.

The above summary of the present invention is not intended to describeeach disclosed embodiment or every implementation of the presentinvention. The description that follows more particularly exemplifiesillustrative embodiments. In several places throughout the application,guidance is provided through lists of examples, which examples can beused in various combinations. In each instance, the recited list servesonly as a representative group and should not be interpreted as anexclusive list.

DETAILED DESCRIPTION

Reaction mixtures used to prepare crosslinked polymeric materials,crosslinked polymeric materials formed from the reaction mixtures,articles containing the crosslinked polymeric materials, methods ofmaking the articles, and methods of immobilizing amine-containingmaterials are described. More specifically, the reaction mixturesinclude (a) a monomer having an amine capture group and (b) acrosslinking monomer. The crosslinked polymeric material has a pendantamine capture group that includes a N-sulfonyldicarboximide groupcapable of reacting with an amine-containing material by a ring openingreaction.

A reaction mixture is provided that includes (a) an amine capturemonomer of Formula I

and (b) a crosslinking monomer that includes at least two (meth)acryloylgroups. The monomer of Formula I can be unsubstituted or substitutedwith a halo, alkyl, alkoxy, or combinations thereof. In Formula I,

-   -   L is an oxy or —NR⁴—;    -   R¹ and R² together with a dicarboximide group to which they are        attached form a four to eight membered heterocyclic or        heterobicyclic group that can be fused to an optional aromatic        group, optional saturated or unsaturated cyclic group, or        optional saturated or unsaturated bicyclic group;    -   R³ is hydrogen or methyl;    -   R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or        alkylsulfonyl; and    -   Y is a divalent group selected from an alkylene, heteroalkylene,        arylene, or combinations thereof.

The amine capture monomer of Formula I can be a (meth)acrylate monomerwhen L is oxy as shown in Formula I(a).

Some exemplary monomers are acrylates (i.e., where R³ is hydrogen) ormethacrylates (i.e., where R³ is methyl).

The amine capture monomer of Formula I can be a (meth)acrylamide monomerwhen L is —NR⁴— as shown in Formula I(b).

Some exemplary monomers are acrylamides (i.e., where R³ is hydrogen) ormethacrylamides (i.e., where R³ is methyl).

The group Y in Formula I is a divalent group that includes an alkylene,heteroalkylene, arylene, or combinations thereof. The group Y canfurther include an optional group selected from a carbonyl, carbonyloxy,carbonylimino, oxy, thio, —NR⁴—, or combination thereof. Group Ytypically does not include peroxide groups (i.e., two oxy groups bondedtogether).

Group Y can be an alkylene or Y can include an alkylene connected to atleast one other group selected from another alkylene, heteroalkylene,arylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, —NR⁴—, orcombination thereof. In other examples, Y can be a heteroalkylene groupor Y can include a heteroalkylene connected to at least one other groupselected from another heteroalkylene, alkylene, arylene, carbonyl,carbonyloxy, carbonylimino, oxy, thio, —NR⁴—, or combination thereof. Instill other examples, Y can be an arylene group or Y can include anarylene connected to at least one other group selected from anotherarylene, alkylene, heteroalkylene, carbonyl, carbonyloxy, carbonylimino,oxy, thio, —NR⁴—, or combination thereof.

The group Y in Formula I often includes an arylene group attacheddirectly to the sulfonyl group as shown Formula I(c):

where Ar¹ is an arylene group and Y¹ is a single bond or a divalentgroup selected from alkylene, heteroalkylene, carbonyl, carbonyloxy,carbonylimino, oxy, thio, —NR⁴—, or combinations thereof. The group—Y¹—Ar¹— in Formula I(c) is equal to —Y— in Formula I. The groups L, R¹,R², R³, and R⁴ are the same as previously defined for Formula I. Theamine capture monomers can be unsubstituted or substituted with a halo,alkyl, alkoxy, or combinations thereof. In some embodiments, the arylenegroup is phenylene.

In some examples of the amine capture monomers of Formula I(c), Y¹ is asingle bond (i.e., L is attached directly to the arylene group). Thatis, Y is an arylene in Formula I. The monomers are of the followingformula

where Ar¹ is an arylene such as phenylene. The other groups are the sameas described above. The amine capture monomers can be unsubstituted orsubstituted with a halo, alkyl, alkoxy, or combinations thereof.

Group Y in Formula I or the group Y¹ in Formula I(c) can include a firstalkylene group linked to an arylene group with a group selected from acarbonyl, carbonyloxy, carbonylimino, oxy, thio, or —NR⁴—. The firstalkylene group can be further linked to a second alkylene or to a firstheteroalkylene group with a group selected from a carbonyl, carbonyloxy,carbonylimino, oxy, thio, or —NR⁴—. Additional alkylene orheteroalkylene groups can be linked to the second alkylene or to thefirst heteroalkylene group with a group selected from a carbonyl,carbonyloxy, carbonylimino, oxy, thio, or —NR⁴—. In some examples, thegroup Y or Y¹ includes an alkylene group linked to an arylene group by acarbonyloxy or carbonylimino group as in the following formulas:

where n is an integer of 1 to 30; and Ar¹ is an arylene group. Exemplarycompounds include those where n is an integer no greater than 24, nogreater than 20, no greater than 10, no greater than 8, no greater than6, or no greater than 4; and Ar¹ is phenylene. The groups R¹, R², R³,and L are the same as previously defined for Formula I. The aminecapture monomers can be unsubstituted or substituted with a halo, alkyl,alkoxy, or combinations thereof.

In another embodiments, group Y or Y¹ can include a first heteroalkylenegroup linked to an arylene with a group selected from a carbonyl,carbonyloxy, carbonylimino, oxy, thio, or —NR⁴—. The firstheteroalkylene group can be further linked to a second heteroalkylene orto a first alkylene group with a group selected from a carbonyl,carbonyloxy, carbonylimino oxy, thio, or —NR⁴—. Additional alkylene orheteroalkylene groups can be linked to the second heteroalkylene or tothe first alkylene group with groups selected from carbonyl,carbonyloxy, carbonylimino group, oxy, thio, or —NR⁴—. In some examples,Y or Y¹ includes a heteroalkylene group linked to an arylene group by acarbonyloxy group as in the following formula:

where m is an integer of 1 to 15; k is an integer of 2 to 4; D is oxy,thio, or —NH—; and Ar¹ is an arylene. The compound can be unsubstitutedor substituted with a halo, alkyl, alkoxy, or combinations thereof. Insome compounds of this formula, m is an integer no greater than 12, nogreater than 10, no greater than 8, no greater than 6, or no greaterthan 4. Exemplary compounds include those where D is oxy; k is equal to2; and Ar¹ is phenylene. The groups L, R¹, R² and R³ are the same aspreviously defined for Formula I. The compounds can be unsubstituted orsubstituted with a halo, alkyl, alkoxy, or combinations thereof.

In some embodiments, Y does not include an arylene group. For example, Ycan be an alkylene group. In another example, a first alkylene group canbe connected to a second alkylene group or to a first heteroalkylenegroup with a group selected from a carbonyl, carbonylimino, carbonyloxy,oxy, thio, or —NR⁴—. Additional alkylene or heteroalkylene groups can beconnected to the second alkylene group or the first heteroalkylene groupwith a group selected from a carbonyl, carbonylimino, carbonyloxy, oxy,thio, or —NR⁴—. In another example, Y can be a heteroalkylene group. Inyet another example, a first heteroalkylene group can be connected to asecond heteroalkylene group or to a first alkylene group with acarbonyl, carbonylimino, carbonyloxy, oxy, thio, or —NR⁴—. Additionalalkylene or heteroalkylene groups can be connected to the secondheteroalkylene group or the first alkylene group with a group selectedfrom a carbonyl, carbonylimino, carbonyloxy, oxy, thio, or —NR⁴—.

In Formula I, R¹ and R² together with the dicarboximide group to whichthey are attached form a four to eight membered heterocyclic orheterobicyclic group that can be fused to an optional aromatic, optionalsaturated or unsaturated cyclic group, or optional saturated orunsaturated bicyclic group. Exemplary structures include, but are notlimited to, the following:

where R is an alkyl and the groups R³, L, and Y are the same aspreviously defined for Formula I. The amine capture monomers can beunsubstituted or substituted with a halo, alkyl, alkoxy, or combinationsthereof.

The amine capture monomers of Formula I often include an arylene groupbonded to the sulfonyl group as in Formula I(c) above. That is, thecompounds can be of the following formulas:

where R is an alkyl; Ar¹ is an arylene; and Y¹ is selected from a singlebond, alkylene, heteroalkylene, carbonyl, carbonyloxy, carbonylimino,oxy, thio, —NR⁴—, or combinations thereof. The group Y¹—Ar¹ is equal togroup Y in Formula I. The groups L, R³, and R⁴ are the same as describedabove for Formula I. In some exemplary amine capture monomers, the groupAr¹ is phenylene. The compounds can be unsubstituted or substituted witha halo, alkyl, alkoxy, or combinations thereof.

Several factors can influence the selection of group Y for a particularapplication. These factors include, for example, ease of synthesis ofthe amine capture monomer, compatibility or reactivity of the aminecapture monomer with the crosslinking monomer, and reactivity orselectivity of the amine capture group with an amine-containingmaterial. For example, the size and the polarity of group Y can affectthe reactivity of the amine capture group with the amine-containingmaterial. That is, the reactivity of the amine capture groups can bealtered by varying the length and composition of group Y. Further, thesize and nature of the ring structure containing the dicarboximide groupcan affect the surface concentration and reactivity withamine-containing materials. The various groups in the amine capturemonomer can be chosen, if desired, to provide a monomer that is liquidat ambient conditions. Liquid monomers tend to be useful in solventlesscoating compositions, which can be environmentally desirable.

The reaction mixtures are often coated from solution and dried (e.g.,close to 100 percent solids) prior to polymerization. Solubility of theamine capture monomer in the solvent and miscibility with thecrosslinking monomer can be important variables for obtaining suitablecoatings. These factors can be controlled by selection of group Y.Heteroalkylene groups tend to improve solubility in polar solvents andmonomers; alkylene groups tend to improve solubility in non-polarsolvents and monomers.

Some specific amine capture monomers according to Formula I include, butare not limited to,

These monomers can be unsubstituted or substituted with a halo, alkyl,alkoxy, or combinations thereof.

Other exemplary amine capture monomers include

where Q¹ is equal to —(CH₂)₃— and Q² is equal to —(CH₂)₂—. Thesemonomers are further described in Japanese Patent Application JP9-54463.

The amine capture monomers contain two reactive functional groups: anamine reactive group that includes the N-sulfonyldicarboximide group anda (meth)acryloyl group that can undergo a free-radical polymerizationreaction. Synthetic strategies must lead to these two reactivefunctional groups but be tolerant of their different reactivity. Theamine capture monomers of Formula I may be prepared, for example, byreaction of a first compound having a nitrogen-containing group with asecond compound that includes a carboxylic acid anhydride. Morespecifically, the nitrogen-containing group of the first compoundincludes a nitrogen atom directly bonded to a sulfonyl group and to twohydrogen atoms. The first compound may further include the(meth)acryloyl group. The reaction is shown in Reaction Scheme A.

where L, Y, R¹, R² and R³ are the same as previously defined for FormulaI.

The reaction mixture typically includes 0.1 to 90 weight percent of theamine capture monomer of Formula I based on the weight of monomers inthe reaction mixture. If less than 0.1 weight percent amine capturemonomer is included in the reaction mixture, there may not be asufficient number of pendant amine capture groups in the resultingcrosslinked polymeric material available for reaction with anamine-containing material. However, if the amount of amine capturemonomer is greater than 90 weight percent, the crosslinked polymer maynot be mechanically robust or dimensionally stable because of the lowamount of crosslinking monomer in the reaction mixture.

The reaction mixture usually contains at least 0.1 weight percent, atleast 0.5 weight percent, at least 1 weight percent, at least 2 weightpercent, at least 5 weight percent, or at least 10 weight percent of theamine capture monomer of Formula I. The reaction mixture typicallycontains up to 90 weight percent, up to 80 weight percent, up to 70weight percent, up to 60 weight percent, up to 50 weight percent, up to40 weight percent, up to 30 weight percent, or up to 20 weight percentof the amine capture monomer. For example, the reaction mixture cancontain 0.2 to 90 weight percent, 0.5 to 90 weight percent, 1 to 90weight percent, 2 to 80 weight percent, 2 to 60 weight percent, 2 to 40weight percent, 2 to 20 weight percent, or 2 to 10 weight percent of theamine capture monomer.

In addition to the monomer of Formula I, the reaction mixture contains acrosslinking monomer that includes at least two (meth)acryloyl groups.Suitable crosslinking monomers include di(meth)acrylates,tri(meth)acrylates, tetra(meth)acrylates, penta(meth)acrylates, and thelike. These (meth)acrylates can be formed, for example, by reacting(meth)acrylic acid with an alkanediols, alkanetriols, alkanetetra-ols,or alkanepenta-ols.

Exemplary crosslinking monomers include 1,2-ethanediol di(meth)acrylate;1,12-dodecanediol di(meth)acrylate; 1,4 butanediol di(meth)acrylate;1,6-hexanediol di(meth)acrylate; trimethylolpropane triacrylate (e.g.,commercially available under the trade designation TMPTA-N from SurfaceSpecialties, Smyrna, Ga. and under the trade designation SR-351 fromSartomer, Exton, Pa.); pentaerythritol triacrylate (e.g., commerciallyavailable under the trade designation SR-444 from Sartomer);tris(2-hydroxyethylisocyanurate) triacrylate (commercially availableunder the trade designation SR-368 from Sartomer); a mixture ofpentaerythritol triacrylate and pentaerythritol tetraacrylate (e.g.,commercially available from Surface Specialties under the tradedesignation PETIA with an approximately 1:1 ratio of tetraacrylate totriacrylate and under the trade designation PETA-K with an approximately3:1 ratio of tetraacrylate to triacrylate); pentaerythritoltetraacrylate (e.g., commercially available under the trade designationSR-295 from Sartomer); di-trimethylolpropane tetraacrylate (e.g.,commercially available under the trade designation SR-355 fromSartomer); ethoxylated pentaerythritol tetraacrylate (e.g., commerciallyavailable under the trade designation SR-494 from Sartomer); anddipentaerythritol pentaacrylate (e.g., commercially available under thetrade designation SR-399 from Sartomer). Mixtures of crosslinkingmonomers can be used.

The reaction mixture can contain 10 to 99.9 weight percent crosslinkingmonomer based on the weight of monomers in the reaction mixture. If lessthan this amount of crosslinking monomer is included in the reactionmixture, the resulting crosslinked polymeric material may not bemechanically robust or dimensionally stable. On the other hand, if agreater amount of crosslinking monomer is used, the number of pendantamine capture groups in the crosslinked polymeric material may be toolow to efficiently react with amine-containing materials.

The amount of crosslinking monomer can be at least 10 weight percent, atleast 15 weight percent, at least 20 weight percent, at least 30 weightpercent, at least 40 weight percent, at least 50 weight percent, atleast 60 weight percent, at least 70 weight percent, at least 80 weightpercent, or at least 90 weight percent. For example, the amount ofcrosslinking monomer can be in the range of 10 to 99 weight percent, 20to 90 weight percent, 30 to 90 weight percent, 30 to 80 weight percent,30 to 70 weight percent, or 30 to 60 weight percent.

Other optional diluent monomers such as (meth)acrylates and(meth)acrylamides can be included in the reaction mixture. Suitablediluent monomers include monomers that do not have an amine capturegroup and that have only one (meth)acryloyl group. The reaction mixturecan include up to 20 weight percent of the diluent monomer based on theweight of monomers in the reaction mixture. If more than about 20 weightpercent diluent monomer is included in the reaction mixture, thecrosslinked polymeric material may not be sufficiently mechanicallyrobust and dimensionally stable or there may not be a sufficient numberof pendant amine capture groups to effectively react withamine-containing compounds. In some reaction mixtures, no diluentmonomer is included. The amount of diluent monomer typically is in therange of 0 to 20 weight percent, 0 to 15 weight percent, 0 to 10 weightpercent, or 0 to 5 weight percent.

Some exemplary (meth)acrylate diluent monomers are alkyl (meth)acrylatessuch as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, tert-butyl methacrylate, n-hexyl(meth)acrylate, cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl(meth)acrylate, 2-methylbutyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, n-octyl(meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate,isodecyl (meth)acrylate, lauryl (meth)acrylate, isononyl (meth)acrylate,isotridecyl (meth)acrylate, and behenyl (meth)acrylate.

Other exemplary (meth)acrylate diluent monomers are aryl (meth)acrylatessuch as phenyl (meth)acrylate, stearyl (meth)acrylate, and benzyl(meth)acrylate. Still other exemplary (meth)acrylate diluent monomersare hydroxy alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylateand 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,glycerol (meth)acrylate, and the like. Additional exemplary(meth)acrylate diluent monomers are ether-containing (meth)acrylatessuch as 2-ethoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,polyethyleneglycol (meth)acrylate, and the like. The diluent monomerscan be nitrogen-containing (meth)acrylates such asN,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, 2-trimethylammoniumethyl (meth)acrylate halides, and thelike. The diluent monomers also can be (meth)acrylamides, N,N-dialkyl(meth)acrylamides, and the like.

Some reaction mixtures contain a solvent. Suitable solvents include, butare not limited to, water, acetonitrile, tetrahydrofuran, ethyl acetate,toluene, acetone, methyl ethyl ketone, isopropanol, N-methylpyrrolidone, chlorinated and fluorinated hydrocarbons, fluorinatedethers, or combinations thereof. Other reaction mixtures can besolventless. Exemplary solventless reaction mixtures include those inwhich the amine capture monomer is a liquid or those in which thereaction mixture is a coated composition with the solvent removed.

A crosslinked polymeric material can be prepared that includes thereaction product of the reaction mixture, as described above, thatcontains (a) an amine capture monomer of Formula I and (b) acrosslinking monomer. These reaction mixtures are typically polymerizedusing a free radical polymerization method. There is often an initiatorincluded in the reaction mixture. The initiator can be a thermalinitiator, a photoinitiator, or both. The initiator is often used at aconcentration of 0.1 to 5 weight percent, 0.1 to 3 weight percent, 0.1to 2 weight percent, or 0.1 to 1 weight percent based on the weight ofmonomers in the reaction mixture.

When a thermal initiator is added to the reaction mixture, thecrosslinked polymer can be formed at room temperature (i.e., 20 to 25degrees Celsius) or at an elevated temperature. The temperature neededfor polymerization often depends on the particular thermal initiatorused. Examples of thermal initiators include organic peroxides or azocompounds.

When a photoinitiator is added to the reaction mixture, a crosslinkedpolymeric material can be formed by the application of actinic radiationuntil the composition gels or hardens. Suitable actinic radiationincludes electromagnetic radiation in the infrared region, visibleregion, ultraviolet region, or a combination thereof.

Examples of photoinitiators suitable in the ultraviolet region include,but are not limited to, benzoin, benzoin alkyl ethers (e.g., benzoinmethyl ether and substituted benzoin alkyl ethers such anisoin methylether), phenones (e.g., substituted acetophenones such as2,2-dimethoxy-2-phenylacetophenone and substituted alpha-ketols such as2-methyl-2-hydroxypropiophenone), phosphine oxides, polymericphotoinitiators, and the like.

Commercially available photoinitiators include, but are not limited to,2-hydroxy-2-methyl-1-phenyl-propane-1-one (e.g., commercially availableunder the trade designation DAROCUR 1173 from Ciba Specialty Chemicals),a mixture of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., commercially availableunder the trade designation DAROCUR 4265 from Ciba Specialty Chemicals),2,2-dimethoxy-1,2-diphenylethan-1-one (e.g., commercially availableunder the trade designation IRGACURE 651 from Ciba Specialty Chemicals),a mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphineoxide and 1-hydroxy-cyclohexyl-phenyl-ketone (e.g., commerciallyavailable under the trade designation IRGACURE 1800 from Ciba SpecialtyChemicals), a mixture ofbis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide (e.g.,commercially available under the trade designation IRGACURE 1700 fromCiba Specialty Chemicals), 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one (e.g., commerciallyavailable under the trade designation IRGACURE 907 from Ciba SpecialtyChemicals), 1-hydroxy-cyclohexyl-phenyl-ketone (e.g., commerciallyavailable under the trade designation IRGACURE 184 from Ciba SpecialtyChemicals),2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (e.g.,commercially available under the trade designation IRGACURE 369 fromCiba Specialty Chemicals), bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (e.g., commercially available under the trade designation IRGACURE819 from Ciba Specialty Chemicals), ethyl 2,4,6-trimethylbenzoyidiphenylphosphinate (e.g., commercially available from BASF, Charlotte, N.C.under the trade designation LUCIRIN TPO-L), and2,4,6-trimethylbenzoyldiphenylphosphine oxide (e.g., commerciallyavailable from BASF, Charlotte, N.C. under the trade designation LUCIRINTPO).

Photoinitiators suitable for use in the visible region often include anelectron donor, and electron acceptor such as an iodonium salt, and avisible light sensitizing compound such as an alpha di-ketone. Suchphotoinitiators are further described, for example, in U.S. PatentPublications 2005/0113477 A1 (Oxman et al.) and 2005/0070627 A1 (Falsafiet al.); and U.S. Pat. No. 6,765,036 B2 (Dede et al.), all incorporatedherein by reference.

An article can be prepared that includes a substrate and a crosslinkedpolymeric material disposed on a surface of the substrate. Thecrosslinked polymeric material is often formed after coating a surfaceof the substrate with a reaction mixture that contains (a) an aminecontaining monomer of Formula I and (b) a crosslinking monomer that hasat least two (meth)acryloyl groups.

The substrates can have any useful form including, but not limited to,films, sheets, membranes, filters, nonwoven or woven fibers, hollow orsolid beads, bottles, plates, tubes, rods, pipes, or wafers. Thesubstrates can be porous or non-porous, rigid or flexible, transparentor opaque, clear or colored, and reflective or non-reflective. Thesubstrates can have a flat or relatively flat surface or can have atextured surface such as wells, indentations, channels, bumps, or thelike. The substrates can have a single layer or multiple layers ofmaterial. Suitable substrate materials include, for example, polymericmaterials, glasses, ceramics, metals, metal oxides, hydrated metaloxides, or combinations thereof.

Suitable polymeric substrate materials include, but are not limited to,polyolefins (e.g., polyethylene and polypropylene), polystyrenes,polyacrylates, polymethacrylates, polyacrylonitriles, polyvinylacetates, polyvinyl alcohols, polyvinyl chlorides, polyoxymethylenes,polycarbonates, polyamides, polyimides, polyurethanes, phenolics,polyamines, amino-epoxy resins, polyesters, silicones, cellulose basedpolymers, polysaccharides, or combinations thereof.

Suitable glass and ceramic substrate materials can include, for example,silicon, aluminum, lead, boron, phosphorous, zirconium, magnesium,calcium, arsenic, gallium, titanium, copper, or combinations thereof.Glasses typically include various types of silicate containingmaterials.

In some embodiments, the substrate includes a layer of diamond-likeglass as disclosed in U.S. Pat. No. 6,696,157 B1 (David et al.), thedisclosure of which is incorporated herein by reference in its entirety.The diamond-like glass is an amorphous material that includes carbon,silicon, and one or more elements selected from hydrogen, oxygen,fluorine, sulfur, titanium, or copper. Some diamond-like glass materialsare formed from a tetramethysilane precursor using a plasma process. Ahydrophobic material can be produced that is further treated in anoxygen plasma to control the silanol concentration on the surface.

Suitable metals, metal oxides, or hydrated metal oxides for substratescan contain, for example, gold, silver, platinum, palladium, aluminum,copper, chromium, iron, cobalt, nickel, zinc, and the like. Themetal-containing material can be alloys such as stainless steel, indiumtin oxide, and the like. In some embodiments, a metal-containingmaterial is the top layer of a multilayer substrate. For example, thesubstrate can have a polymeric second layer and a metal containing firstlayer. In one example, the second layer is a polymeric film and thefirst layer is a thin film of gold. In other examples, a multilayersubstrate includes a polymeric film coated with a titanium-containinglayer and then coated with a gold-containing layer. That is, thetitanium layer can function as a tie layer or a primer layer foradhering the layer of gold to the polymeric film. In other examples of amultilayer substrate, a silicon support layer is covered with a layer ofchromium and then with a layer of gold. The chromium layer can improvethe adhesion of the gold layer to the silicon layer.

The articles can be prepared by providing a substrate, disposing areaction mixture on a surface of the substrate, and curing the reactionmixture to form a crosslinked polymeric material. The reaction mixturecontains (a) an amine capture monomer of Formula I and (b) acrosslinking monomer, as described above. The reaction mixture can becured, for example, through the application of heat (i.e., a thermalinitiator is used) or through the application of actinic radiation(i.e., a photoinitiator is used).

The reaction mixture can often wet the surface of the substrate and theresulting crosslinked polymer adheres to the surface of the substrate.The crosslinked polymer usually adheres without the formation of acovalent bond between a reactive group on the polymer and acomplementary group on the surface of the substrate. Rather, the polymeradheres by interlocking with surface imperfections on the substrate.

In some articles, the crosslinked polymeric material is patterned on thesubstrate. Any suitable pattern of the crosslinking polymeric materialcan be formed. For example, the pattern can be in the form of text,design, image, or the like. The pattern can be, for example, in the formof dots, squares, rectangles, lines, circles or waves (e.g., squarewaves, sinusoidal waves, and sawtooth waves).

One method of forming a patterned crosslinked polymeric layer includesdisposing a pattern of the reaction mixture on the surface of thesubstrate by screen printing, jet printing (e.g., spray jet, valve jet,or ink jet printing), and the like. Useful devices for jet printing aredescribed, for example, in U.S. Pat. No. 6,513,897 (Tokie) and in U.S.Patent Publication No. 2002/0128340 (Young et al.), both incorporatedherein by reference. After application of the pattern to the surface ofthe substrate, the reaction mixture can be cured. For example, thereaction mixture can be cured by application of heat if a thermalinitiator is included in the reaction mixture or by application ofactinic radiation if a photoinitiator is included in the reactionmixture.

Another method of forming a patterned crosslinked polymeric layerincludes forming a layer of the reaction mixture on the substrate,curing a first portion of the reaction mixture to form a pattern ofcrosslinked polymeric material on the substrate, and removing a secondportion of the reaction mixture that is not cured. The layer of reactionmixture on the substrate can be prepared using any suitable techniquesuch as, for example, brush coating, spray coating, gravure coating,transfer roll coating, knife coating, curtain coating, wire coating, anddoctor blade coating.

One method of polymerizing a portion of the reaction mixture involvesthe use of a photoinitiator in the reaction mixture and the use ofmasks. The mask contains a pattern of openings and can be positionedbetween the layer of reaction mixture and the actinic radiation source.Actinic radiation can pass through the openings in the mask. Uponexposure to actinic radiation, a first portion of the reaction mixturelayer corresponding to the openings in the mask can polymerize and asecond portion of the reaction mixture layer that is blocked from theactinic radiation by the mask remains uncured or not reacted. That is,the uncured reaction mixture is a monomeric composition that has notgelled or hardened to form a crosslinked polymeric material. The uncuredreaction mixture can be removed using a suitable solvent for themonomers of Formula I, the crosslinking monomers, and any optionaldiluent monomers. The solvent typically does not dissolve the curedcrosslinked polymeric material because of the extensive crosslinking.Thus, the uncured reactive mixture can be removed leaving a pattern ofcrosslinked polymeric material on the substrate surface.

Suitable solvents for removing the unreacted reaction mixture include,but are not limited to, water, acetonitrile, tetrahydrofuran, ethylacetate, toluene, acetone, methyl ethyl ketone, isopropanol, N-methylpyrrolidone, chlorinated and fluorinated hydrocarbons, fluorinatedethers, or combinations thereof. The crosslinked polymeric material istypically insoluble in these solvents. As used herein, an insolublepolymer is one that has a solubility at room temperature that is lessthan 0.01 weight percent in a solvent such as, for example, water,acetonitrile, tetrahydrofuran, ethyl acetate, toluene, acetone, methylethyl ketone, isopropanol, N-methyl pyrrolidone, chlorinated andfluorinated hydrocarbons, fluorinated ethers, or combinations thereof.

Suitable masks for this method of patterning include polymeric materials(e.g., polyesters such as polyethylene terephthalate or polyethylenenaphthalate, polyimide, polycarbonate, or polystyrene), metal foilmaterials (e.g., stainless steel, other steels, aluminum, or copper),paper, woven or nonwoven fabric materials, or combinations thereof.Polymeric masks and the openings in these masks are further described inU.S. Pat. No. 6,897,164 B2 (Baude et al.), incorporated herein byreference. The openings in the mask can be of any suitable dimension.

The crosslinked polymeric material has pendant amine capture groups.Thus, an article having a layer or pattern of crosslinked polymericmaterial on a surface of a substrate can have amine capture groups thatare capable of reacting with an amine-containing material. The pendantamine capture groups of the polymeric material are of Formula II

attached to the backbone of the crosslinked polymeric backbone. Thegroups L, Y, R¹, and R² are previously described for Formula I. Theasterisk (*) in Formula II indicates the location where the pendantamine capture group is attached to the backbone of the crosslinkedpolymeric material. The pendant amine capture groups include aN-sulfonyldicarboximide group.

The pendant groups according to Formula II usually have improvedhydrolytic stability compared to derivatives of N-hydroxysuccinimide,which are groups known to react with amine-containing materials. Becauseof the improved hydrolytic stability of the pendant groups of FormulaII, the crosslinked polymeric materials and articles containing thecrosslinked polymeric material typically can be used in aqueous systems.

The amine capture groups can be reacted with an amine-containingmaterial resulting in the immobilization of the amine-containingmaterial. A method of immobilizing an amine-containing material includesproviding a substrate, and disposing a reaction mixture on a surface ofthe substrate. The reaction mixture contains (a) a monomer of Formula Iand (b) a crosslinking monomer that includes at least two (meth)acryloylgroups. The method further includes curing the reaction mixture to forma crosslinked polymeric material having a pendant amine capture group,and reacting an amine-containing material with the pendant amine capturegroup of the crosslinked polymeric material. In this method, theN-sulfonyldicarboximide group in the pendant amine capture group canreact with an amine-containing material. In some embodiments, theamine-containing materials are biomolecules such as, for example, aminoacid, peptide, DNA, RNA, protein, enzyme, organelle, cell, tissue,immunoglobin, or a fragment thereof. In other embodiments, theamine-containing material is a non-biological amine such as anamine-containing analyte.

The amine-containing material can react with the pendant amine capturegroup by a ring opening reaction with the N-sulfonyldicarboximide group.The amine-containing material can have a primary amine group or asecondary amine group. For example, the amine-containing material can bea primary amine-containing biological material of formula H₂N-T where Tis the remainder of the primary amine-containing biological material(i.e., the group T is equal to a primary amine-containing biologicalmaterial of formula H₂N-T minus the —NH₂ group). Group T often has analkylene group attached directly to the —NH₂ group. The primaryamine-containing biological material reacts with the crosslinkedpolymeric material having pendant groups of Formula II to produce acrosslinked polymeric material having a reacted pendant group of FormulaIII:

Group R⁵, which corresponds to the combined groups R¹ and R² in FormulasI and II, is an alkylene having 1 to 5 carbon atoms, aromatic group,saturated or unsaturated cyclic group, saturated or unsaturated bicyclicgroup, or combination thereof. The groups L, Y, and * are the same aspreviously defined for Formulas I and II. The presence of theimmobilized amine can be determined, for example, using massspectroscopy, contact angle measurement, infrared spectroscopy, andellipsometry. Additionally, various immunoassays and optical microscopictechniques can be used if the amine-containing material is abiologically active material.

The rate of reaction of amine-containing materials with theN-sulfonyldicarboximide groups of the pendant amine capture groups ofFormula II is typically faster than the rate of hydrolysis of theN-sulfonyldicarboximide group. That is, immobilization ofamine-containing materials occurs at a faster rate than the hydrolysisreactions. The amine-containing materials are not easily displaced onceimmobilization to a pendant group of the crosslinked polymeric materialhas occurred due to the formation of a covalent carbonylimino bond.

Immobilized biological amine-containing materials can be useful in themedical diagnosis of a disease or of a genetic defect. The immobilizedamine-containing materials can also be used for biological separationsor for detection of the presence of various biomolecules. Additionally,the immobilized amine-containing materials can be used in bioreactors oras biocatalysts to prepare other materials. The pendant groups with theN-sulfonylaminocarbonyl groups also can be used to detectamine-containing analytes that are not biological materials. Theamine-containing analytes can have primary amine groups, secondary aminegroups, or a combination thereof.

Other materials can be further bound to the immobilized amine-containingmaterial. This further bound material can be associated with theamine-containing material before immobilization of the amine-containingmaterial or can be bound to the amine-containing material subsequent toimmobilization of the amine-containing material. The amine-containingmaterial and the further bound material can be complementary RNAfragments, complementary DNA fragments, an antigen-antibody combination,an immunoglobin-bacterium combination, and the like.

Biological amine-containing materials often can remain active afterattachment to the pendant group of the crosslinked polymeric material(i.e., the pendant groups according to Formula III can includebiologically active amine-containing materials). For example, animmobilized antibody can subsequently bind to an antigen or animmobilized antigen can subsequently bind to an antibody. Similarly animmobilized amine-containing biological material that has a portion thatcan bind to a bacterium can subsequently bind to the bacterium (e.g., animmobilized immunoglobulin can subsequently bind to a bacterium such asStaphylococcus aureus).

The pendant groups of Formula II and Formula III are attached to thebackbone of a crosslinked polymeric material. The crosslinked polymericmaterial is formed by a free radical polymerization reaction of(meth)acryloyl groups. A crosslinked polymeric material with pendantgroups of Formula II can be further crosslinked by reaction of a primaryamine containing material having at least two primary amine groups,secondary amine groups, or a combination thereof. That is, an aminecontaining material that has more than one primary amine or secondaryamine groups may react with more than one pendant group of Formula II.

EXAMPLES

These examples are merely for illustrative purposes only and are notmeant to be limiting on the scope of the appended claims. All parts,percentages, ratios, etc. in the examples and the rest of thespecification are by weight, unless noted otherwise. Solvents and otherreagents used were obtained from Sigma-Aldrich Chemical Company;Milwaukee, Wis. unless otherwise noted. Table of AbbreviationsAbbreviation or Trade Designation Description ACN Acetonitrile DMFDimethylformamide NMP N-methylpyrrolidinone THF Tetrahydrofuran TMPTATrimethylolpropane triacrylate Photoinitiator DAROCUR 1173 Photo curingagent 2-hydroxy-2- methyl-1-phenyl-1-propanone, available from Ciba;Hawthorne, NJ DI water Deionized water PEI Polyethyleneimine IPAIsopropyl alcohol TWEEN-25 Polyoxyethylenesorbitan monolaurate fromSigma, St Louis, MO

Preparative Example 1

Preparation of

In a glass reaction vessel, a mixture of DMF (154 milliliters),4-carboxybenzenesulfonamide (30.0 grams), succinic anhydride (16.41grams), and triethylamine (33.19 grams) was stirred and heated to 50° C.under a nitrogen atmosphere for four hours. The mixture was allowed tocool to room temperature, acetic anhydride (18.27 grams) was added andthe mixture was stirred at room temperature for an additional threehours. The mixture was poured into 400 milliliters of stirred 1N aqueousHCl. This mixture was filtered, washed with deionized water and dried ina vacuum oven to afford the desired product. Yield: 36.94 grams.

Preparative Example 2

Preparation of

In a glass reaction vessel containing a stirred mixture of thecarboxy-containing product of Preparative Example 1 (20.0 grams) and dryacetonitrile (85 grams) was added thionyl chloride (10.0 grams) and DMF(1 drop). The resulting mixture was stirred and heated under reflux forone hour, cooled to room temperature and further cooled in an ice bath,which resulted in the formation of a solid precipitate. The solid wascollected by filtration, washed sequentially with cold acetonitrile andcold toluene, and dried overnight in a vacuum oven at 50° C. to give thedesired product. Yield: 17.7 grams.

Preparative Example 3

Preparation of

In a glass reaction vessel a mixture of NMP (9.11 milliliters),2-hydroxyethyl methacrylate (0.78 grams) and a sample of the carbonylchloride product of Preparative Example 2 (1.50 grams) were combined andstirred overnight at room temperature. The mixture was poured into 0.1NHCl and the resultant solid was collected by filtration, washed withdeionized water, and dried in a vacuum oven at room temperatureovernight at 133.3 Pa (1 mm Hg) to give the desired product. Yield: 1.53grams.

Preparative Example 4

Preparation of Mixture of

A solution of a sample of the acid chloride product of PreparativeExample 2 (4.58 grams) in ACN (6.6 grams) was placed in a glass reactionvessel under a nitrogen atmosphere and chilled with an ice bath. To thisstirred solution was added a solution of 2-hydroxypropyl acrylate (2.07grams) and triethylamine (1.69 grams) in ACN (20.0 grams). The mixturewas stirred for overnight and allowed to warm to room temperature. Themixture was poured into 0.1N aqueous HCl and the resultant solid wascollected by filtration, washed with deionized water, and dried in avacuum oven at room temperature overnight at 133.3 Pa (1 mm Hg) to givethe desired product.

Preparative Example 5

Preparation of

Pyridine (5.93 grams) was added to a solution of sulfanilamide (10.75grams) in THF (85.4 milliliters) within a glass reaction vessel chilledin an ice bath. Methacrylic anhydride (10.10 grams) was added and themixture was stirred overnight while warming to room temperature. Thereaction mixture was filtered and the resulting solid was dried in avacuum oven at room temperature overnight at 133.3 Pa (1 mm Hg) to givethe desired product. Yield: 8.4 grams.

Preparative Example 6

Preparation of

A solution of a sample of the product of Preparative Example 5 (6.00grams), acetic anhydride (2.75 grams), and triethylamine (3.34 grams) inACN (40 milliliters) with a trace of phenothiazine was placed in a glassreaction vessel fitted with a reflux condenser. This mixture wasrefluxed for 6 hours, cooled to room temperature, succinic anhydride(3.25 grams) and triethylamine (6.11 grams) were added and the mixturewas refluxed for 1 hour. The mixture was poured into 0.1N aqueous HCland the resultant solid was collected by filtration, washed withdeionized water, and dried in a vacuum oven at room temperatureovernight at 133.3 Pa (1 mm Hg) to give the desired product. Yield: 5.9grams.

Preparative Example 7

Preparation of

A 3-neck round bottom flask, fitted with a reflux condenser, athermometer, a pressure-equalizing addition funnel, a magnetic stir bar,and a hose adapter connected to a source of nitrogen gas, was chargedwith 22.52 grams of a 60 weight percent dispersion of NaH in mineraloil. The dispersion was washed three times with heptane by stirring themixture for several minutes, allowing the mixture to stand, and thenusing a pipette to remove the supernatant heptane. NMP (32 grams) wasadded to the flask and the mixture was stirred. A solution of camphoricanhydride (11.7 grams), sulfanilamide (10 grams), and NMP (50 grams) wasslowly added to the flask using the addition funnel. The mixture wasthen stirred at room temperature for 24 hours. The mixture was combinedwith 0.1N aqueous HCl and this mixture was extracted with ethyl acetate.The extract was dried over MgSO₄ and the volatile components wereremoved using a rotary evaporator. This intermediate material wascombined with methanesulfonyl chloride (6.98 grams), triethylamine(13.51 grams), and DMF (82.4 grams) in a round bottom flask. The mixturewas magnetically stirred for 1 hour at 60° C. The mixture was thenpoured into aqueous 1N HCl within a beaker and the resultant solid wasisolated by filtration. The solid was recrystallized from methanol toafford 3 grams of product.

Preparative Example 8

Preparation of

A solution of the product of Preparative Example 7 (1.20 grams) andpyridine (0.34 grams) in dry THF (4.3 grams) was slowly added to asolution of acryloyl chloride (0.39 grams) in dry THF (2.0 grams) withina glass reaction vessel under a nitrogen atmosphere and chilled with anice bath. The mixture was stirred overnight and allowed to warm to roomtemperature. The solvent was partially removed using a rotaryevaporator. The mixture was poured into 0.1N aqueous HCl and theresultant solid was collected by filtration, washed with deionizedwater, and dried in a vacuum oven at room temperature overnight at 133.3Pa (1 mm Hg) to give the desired product. Yield: 0.80 grams.

Preparative Example 9

Preparation of

A 3-neck round bottom flask, fitted with a reflux condenser, athermometer, a pressure-equalizing addition funnel, a magnetic stir bar,and a hose adapter connected to a source of nitrogen gas, was chargedwith 16.22 grams of a 60 weight percent dispersion of NaH in mineraloil. The dispersion was washed three times with heptane by stirring themixture for several minutes, allowing the mixture to stand, and thenusing a pipette to remove the supernatant heptane. NMP (50 grams) wasthen added to the flask and the mixture was stirred. A solution ofcamphoric anhydride (14 grams), 4-carbomethoxybenzenesulfonamide (15grams), and NMP (61 grams) was slowly added to the flask using theaddition funnel. The mixture was then stirred at room temperature forapproximately 1 hour and then poured into 0.1N aqueous HCl within abeaker. This mixture was then extracted with ethyl acetate, dried overmagnesium sulfate, and the volatile components were removed using arotary evaporator to afford a solid intermediate.

The intermediate was combined with THF (111 grams), acetic anhydride(8.54 grams), and triethylamine (23.3 grams) and then stirred for 1 hourat 60° C. The mixture was then poured into aqueous 1N HCl in a beakerand the resultant solid was isolated by filtration. The solid wascombined with methanol and this mixture was heated to boiling, cooled toroom temperature, filtered, and washed sequentially with methanol anddiethyl ether. The solid was dried overnight in a vacuum oven at roomtemperature and 67 Pa (0.5 mm Hg) to afford the product.

Preparative Example 10

Preparation of

A 3-neck round bottom flask, fitted with a magnetic stir bar, refluxcondenser, digital temperature probe, rubber septum, and a hose adapterconnected to a source of nitrogen gas, was charged with a mixture of thecarboxylic acid product of Preparative Example 9 and acetonitrile (20grams). The flask was placed in an ice bath and a 20 weight percentsolution of phosgene in toluene (15.57 grams) that was obtained fromFluka Holding AG, Buchs, Switzerland was added slowly via syringe. Themixture was then allowed to warm to room temperature and then heated atreflux. Periodically, the atmosphere above the reaction mixture wastested for the presence of hydrogen chloride using moist pH paper. Whenno phosgene could be detected in this way, the flask was fitted with adistillation head and a small amount of the volatile materials weredistilled away. The mixture was then filtered and the solid was driedunder a stream of nitrogen gas to afford the product.

Preparative Example 11

Preparation of

In a glass reaction vessel, a solution of 2-hydroxyethyl methacrylate(0.68 grams) and a sample of the acid chloride product of PreparativeExample 10 (1.68 grams) in NMP (9.45 milliliters) was stirred overnightat room temperature. The mixture was poured into aqueous 0.1N HCl andextracted with ethyl acetate. The organic phase was washed successivelywith deionized water and saturated aqueous NaCl and dried over MgSO₄.The solution was concentrated using a rotary evaporator and driedovernight in a vacuum oven at room temperature and 67 Pa (0.5 mm Hg) togive the desired product. Yield: 1.8 grams.

Preparative Example 12

Preparation of

To a 3-neck round bottom flask, fitted with a reflux condenser, athermometer, a pressure-equalizing addition funnel, a magnetic stir bar,and a hose adapter connected to a source of nitrogen gas, was addedsulfanilamide (20 grams), pyridine (11.02 grams) and THF (59 grams). Tothis stirred mixture was added methanesulfonyl chloride (14.63 grams)dropwise via the addition funnel. After stirring overnight at roomtemperature, the reaction mixture was poured into water and theresultant solid was isolated by filtration. The solid was driedovernight in a vacuum oven at room temperature and 67 Pa (0.5 mm Hg) toafford 26.3 grams of product.

Preparative Example 13

Preparation of

A solution of a sample of the product of Preparative Example 12 (10.75grams), succinic anhydride (5.64 grams), and triethylamine (5.21 grams)in DMF (38.23 grams) was placed in a glass reaction vessel fitted with areflux condenser. This mixture was heated to 50° C. in an oil bath for 4hours. The mixture was cooled to room temperature, acetic anhydride(4.60 grams) and triethylamine (5.01 grams) were added and the mixturewas stirred. The mixture was poured into water and the resultant solidwas collected by filtration, washed with deionized water, and dried in avacuum oven at room temperature overnight at 133.3 Pa (1 mm Hg) to givethe desired product. Yield: 10.56 grams.

Preparative Example 14

Preparation of

In a glass vessel the product of Preparative Example 13 (1.00 gram) wasdissolved in ACN (4.6 grams) and triethylamine (0.33 gram). To thisstirred solution was added acryloyl chloride (0.26 gram) dropwise viapipette. The mixture, after stirring for 1 hour at room temperature, waspoured into water and the resultant solid was collected by filtration,washed with deionized water, and dried in a vacuum oven at roomtemperature overnight at 133.3 Pa (1 mm Hg) to give the desired product.

Preparation of PEI Coated Glass Slide Matrix

Glass microscope slides were soaked for two hours in a 5 Molar NaOHbath; rinsed with DI water, ethanol, and methanol; and dried under astream of nitrogen. The clean slides were kept in an 80° C. oven untilneeded.

Eight of the slides were arranged in a matrix of 2 columns and 4 rows.The slides were secured in position within the matrix using a strip oftape down the middle of the back side of each slide. A 2 weight percentsolution of PEI in IPA was coated onto the matrix using a number 12Mayer rod. The coating was allowed to dry in air.

Preparation of IgG labeled with Cy5

The contents of three vials of Cy5 dye (3H-Indolium,2-[5-[1-[6-[(2,5-dioxo-1-pyrrolidinyl)oxy]-6-oxohexyl]-1,3-dihydro-3,3-dimethyl-5-sulfo-2H-indol-2-ylidene]-1,3-pentadienyl]-1-ethyl-3,3-dimethyl-5-sulfo-,inner salt (9CI)) were dissolved in dimethylsulfoxide (DMSO) to a totalvolume of 100 microliters. The vials of Cy5 dye were obtained fromGE-Amersham Biosciences, Piscataway N.J. The resulting dye solution wasadded to 1 milliliter of a 5 milligrams/milliliter solution of mouse IgGin 0.1 M sodium carbonate (at pH 9.0). The mouse IgG was obtained fromSigma, St. Louis, Mo. The resulting solution was protected from lightexposure and gently rocked for 45 minutes at room temperature. Thissolution contained Cy5-labelled antibody and unreacted Cy5.

Cy5-labelled antibody (Cy5-IgG) was separated from unreacted Cy5 labelusing gel filtration chromatography. The solution containing the Cy5-IgGand unreacted Cy5 was added to a PD-10 column that was equilibratedusing phosphate buffer solution (PBS) at pH 7.4. The PD-10 column wasobtained from GE-Amersham Biosciences, Piscataway N.J. The Cy5-IgGfraction was collected by washing with PBS at pH 7.4. The Cy5/IgG ratiowas calculated by measuring the IgG concentration (280 nm) and the Cy5concentration (650 nm) in the Cy5-IgG fraction. The productspecifications provided by the manufacturer of Cy5 and IgG were followedto obtain the extinction coefficient values for IgG and Cy5 as well asthe absorbance contribution from covalently bound Cy5 at 280 nm. Thefinal Cy5-IgG solution had a concentration 1.3 milligrams/milliliterCy5-IgG with a Cy5/IgG ratio of 2.2. From this stock solution, testsolutions containing 130, 50, 13 and 5 micrograms/milliliters of Cy5-IgGin 10 millimolar carbonate buffer at pH 9.6 were prepared. The bufferwas prepared using sodium carbonate/sodium bicarbonate buffer capsulesavailable from Sigma, St. Louis, Mo.

Comparative Example C1

A solution of Photoinitiator (0.01 gram) and TMPTA (0.6 gram) in ACN (5grams) was prepared. This solution contained 11 weight percent TMPTA and0.18 weight percent Photoinitiator based on the weight of the solution.This solution was coated onto a PEI coated glass slide matrix, which isdescribed above, using a number 12 Mayer rod. The coating was allowed todry in air. The coated matrix was passed twice through a curingapparatus at a rate of 50 feet/minute (15 meters/minute). The curingapparatus was obtained from Fusion Systems of Gaithersburg, Md. and wasequipped with a F300 lamp. The resulting cured coating was rubbed with ametal spatula to ensure the coating could not be rubbed off.

Spots of 5 microliters of the Cy5-IgG test solutions prepared above anda sample without Cy5-IgG were applied to the coated surface and allowedto sit for 30 minutes. The surface was rinsed with 0.25 weight percentTWEEN-25 in DI water and then rinsed with DI water. The slides weredried under nitrogen and placed into a fluorescence reader, which iscommercially available from Tecan Group LTD, Research Triangle Park,N.C. under the trade designation LS SERIES TECAN. Single scanmeasurements were made by adjusting the focal height to 1002micrometers, 40 micrometers resolution, oversampling of 3 micrometers, again of 160, and a pinhole depth focus of ±150 micrometers. The data wasanalyzed as 16-bit pixelized TIFF files using software commerciallyavailable from Molecular Devices Corp, Sunnyvale, Calif. under the tradedesignation GENEPIX PRO. The data are shown in Table 1.

Example 1

A solution was prepared by dissolving the material from PreparativeExample 14 (0.03 gram), Photoinitiator (0.01 gram), and TMPTA (0.56gram) in ACN (5 grams). The resulting solution contained 0.5 weightpercent Preparative Example 1, 0.18 weight percent Photoinitiator, and10 weight percent TMPTA based on the weight of the solution. Thissolution was coated onto a PEI coated glass slide matrix describedabove, using a number 12 Mayer rod. The resulting coating was allowed todry in air. The coated matrix was passed twice at a rate of 50feet/minute (15 meters/minute) through the Fusion Systems curingapparatus equipped with a F300 lamp. The resulting cured coating wasrubbed with a metal spatula to ensure the coating could not be rubbedoff.

Five microliter spots of the Cy5-IgG test solutions and of a samplewithout Cy5-IgG were made onto the coated surface and allowed to sit for30 minutes. The surface was rinsed with 0.25 weight percent TWEEN-25 inDI water and then with DI water. The slides were dried under nitrogenand placed into a fluorescence reader, which is commercially availablefrom Tecan Group LTD, Research Triangle Park, N.C. under the tradedesignation LS SERIES TECAN. Single scan measurements were made byadjusting the focal height to 1002 micrometers and using 40 micrometersresolution, a gain of 160, oversampling of 3 micrometers, and a pinholedepth focus of ±150 micrometers. The data was analyzed as 16-bitpixelized TIFF files using software commercially available fromMolecular Devices Corp, Sunnyvale, Calif. under the trade designationGENEPIX PRO. The data are shown in Table 1.

Example 2

A solution was prepared by dissolving the material of PreparativeExample 3 (0.03 gram), Photoinitiator (0.01 gram), and TMPTA (0.56 gram)in ACN (5.25 grams). The resulting solution contained 0.5 weight percentPreparative Example 2, 0.18 weight percent photoinitiator, and 10 weightpercent TMPTA based on the weight of the solution. This solution wascoated onto a PEI coated glass slide matrix described above using anumber 12 Mayer rod. The resulting coating was allowed to dry in air.

The coated matrix was passed twice through the Fusion Systems curingapparatus equipped with a F300 lamp at a rate of 50 feet/minute (15meters/minute). The resulting cured coating was rubbed with a metalspatula to ensure the coating could not be rubbed off.

Five microliter spots of the Cy5-IgG test solutions and of a samplewithout Cy5-IgG were applied to the coated surface and allowed to sitfor 30 minutes. The surface was rinsed with 0.25 weight percent TWEEN-25in DI water and then with DI water. The slides were dried under nitrogenand placed into a fluorescence reader, which is commercially availablefrom Tecan Group LTD, Research Triangle Park, N.C. under the tradedesignation LS SERIES TECAN. Single scan measurements were made byadjusting the focal height to 1002 micrometers and using 40 micrometersresolution, a gain of 160, oversampling of 3 micrometers, and a pinholedepth focus of ±150 micrometers. The data was analyzed as 16-bitpixelized TIFF files using software commercially available fromMolecular Devices Corp, Sunnyvale, Calif. under the trade designationGENEPIX PRO. The data are shown in Table 1. TABLE 1 Concentration ofFluorescence Fluorescence Fluorescence Cy5-IgG Measurement MeasurementMeasurement (Micrograms/milliliter) Example C1 Example 1 Example 2 13034108 63487 46879  50 17295 23197 NM 13 8135 10518 8183 5 1270 3644 49440 1266 200 3012NM = not measured*Note the value of 65535 is the maximum number of pixels that can bemeasured using a 16-bit fluorescence reader.

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

1. A reaction mixture comprising: a) an amine capture monomer of Formula I:

wherein L is an oxy or —NR⁴—; R¹ and R² together with a dicarboximide group to which they are attached form a four to eight membered heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group; R³ is hydrogen or methyl; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; the monomer of Formula I is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and b) a crosslinking monomer comprising at least two (methyl)aryloyl groups.
 2. The reaction mixture of claim 1, wherein the amine capture monomer is of Formula I(a)


3. The reaction mixture of claim 1, wherein the amine capture monomer is of Formula I(b)


4. The reaction mixture of claim 1, wherein the amine capture monomer is of Formula I(c)

wherein Ar¹ is an arylene group; and Y¹ is a single bond or a divalent group selected from alkylene, heteroalkylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, —NR⁴—, or combinations thereof.
 5. The reaction mixture of claim 1, wherein the amine capture monomer is selected from


6. The reaction mixture of claim 1, wherein the amine capture monomer is selected from

wherein R is an alkyl; Ar¹ is an arylene; and Y¹ is selected from a single bond, alkylene, heteroalkylene, carbonyl, carbonyloxy, carbonylimino, oxy, thio, —NR⁴, or combinations thereof.
 7. The reaction mixture of claim 1, wherein the amine capture monomer is selected from


8. The reaction mixture of claim 1, further comprising a photoinitiator, a thermal initiator, or a combination thereof.
 9. The reaction mixture of claim 1, wherein Y further comprises a group selected from a carbonyl, carbonyloxy, carbonylimino, oxy, thio, —NR⁴—, or combinations thereof.
 10. A crosslinked polymeric material comprising the reaction product of a reaction mixture comprising: a) an amine capture monomer of Formula I

wherein L is an oxy or —NR⁴—; R¹ and R² together with a dicarboximide group to which they are attached form a four to eight membered heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group; R³ is hydrogen or methyl; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; the monomer of Formula I is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and b) a crosslinking monomer comprising at least two (meth)acryloyl groups.
 11. An article comprising a substrate; and a crosslinked polymeric material disposed on a surface of the substrate, the crosslinked polymeric material having a pendant amine capture group comprising a N-sulfonyldicarboximide group and the crosslinked polymeric material being the reaction product of a reaction mixture comprising: a) an amine capture monomer of Formula I

wherein L is an oxy or —NR⁴—; R¹ and R² together with a dicarboximide group to which they are attached form a four to eight membered heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group; R³ is hydrogen or methyl; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; the monomer of Formula I is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and b) a crosslinking monomer comprising at least two (meth)acryloyl groups.
 12. A method of immobilizing an amine-containing material to a substrate, the method comprising providing a substrate; disposing a reaction mixture on a surface of the substrate, the reaction mixture comprising: a) an amine capture monomer of Formula I

wherein L is an oxy or —NR⁴—; R¹ and R² together with a dicarboximide group to which they are attached form a four to eight membered heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group; R³ is hydrogen or methyl; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; the monomer of Formula I is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and b) a crosslinking monomer comprising at least two (meth)acryloyl groups; curing the reaction mixture to form a crosslinked polymeric material having a pendant amine capture group comprising a N-sulfonyldicarboximide group; and reacting an amine-containing material with the N-sulfonyldicarboximide group.
 13. The method of claim 12, wherein the amine-containing material is an amine-containing analyte, amino acid containing analyte, an amino acid, peptide, DNA, RNA, protein, enzyme, organelle, cell, tissue, immunoglobulin, or fragment thereof.
 14. The method of claim 12, wherein the amine-containing material is an antibody and the antibody is further bound to an antigen.
 15. The method of claim 12, wherein the amine-containing material is an antigen and the antigen is further bound to an antibody.
 16. The method of claim 12, wherein the amine-containing material is an immunoglobulin and the immunoglobin is further bound to a bacterium.
 17. A method of making an article, the method comprising providing a substrate; disposing a reaction mixture on a surface of the substrate, the reaction mixture comprising: a) an amine capture monomer of Formula I

wherein L is an oxy or —NR⁴—; R¹ and R² together with a dicarboximide group to which they are attached form a four to eight membered heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group; R³ is hydrogen or methyl; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; and Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; the monomer of Formula I is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and b) a crosslinking monomer comprising at least two (meth)acryloyl groups; and curing the reaction mixture to form a crosslinked polymeric material having a pendant amine capture group comprising a N-sulfonyldicarboximide group.
 18. The method of claim 17, further comprising reacting the N-sulfonyldicarboximide group with a nitrogen-containing material having a primary amine group, a secondary amine group, or a combination thereof.
 19. A polymeric material comprising a pendant group of Formula II

wherein L is an oxy or —NR⁴—; R¹ and R² together with a dicarboximide group to which they are attached form a four to eight membered heterocyclic or heterobicyclic group that can be fused to an optional aromatic group, optional saturated or unsaturated cyclic group, or optional saturated or unsaturated bicyclic group; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; an asterisk (*) denotes an attachment site of the pendant group to a backbone of the polymeric material; the pendant group of Formula II is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and the polymeric material is crosslinked.
 20. A polymeric material comprising a pendant group of Formula III

L is an oxy or —NR⁴—; R⁴ is hydrogen, alkyl, aryl, aralkyl, acyl, arylsulfonyl, or alkylsulfonyl; R⁷ is an alkylene having 1 to 5 carbon atoms, aromatic group, saturated or unsaturated cyclic group, saturated or unsaturated bicyclic group, or combination thereof; T is equal to a primary amine-containing biological material minus a —NH₂ group; Y is a divalent group comprising an alkylene, heteroalkylene, arylene, or combinations thereof; an asterisk (*) denotes an attachment site of the pendant group to a backbone of the polymeric material; the pendant group of Formula III is unsubstituted or substituted with a halo, alkyl, alkoxy, or combinations thereof; and the polymeric material is crosslinked. 